JPH1180529A - Flame-retardant polycarbonate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent heat resistance and heat stability and improved safety, useful as an optical material, etc., by adding an organic sulfonate, etc., in an amount to make a specific polycarbonate copolymer flame-retardant. SOLUTION: This composition is obtained by compounding a polycarbonate copolymer comprising 5-95 mol.% of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 95-5 mol.% of a hydroxyl component of the formula (R<1> to R<4> are each H, a 1-9C hydrocarbon, etc. W is a single bond, a 1-20C hydrocarbon, etc.) [e.g. 2,2,-bis(4-hydroxyphenyl)propane, etc.] per the whole aromatic dihydroxyl component with one or more compounds (e.g. potassium sulfonate of diphenylsulfone, thorium lauryl sulfate, triphenyl phosphate, etc.) selected from an organic sulfonate, an organic sulfuric acid ester salt, a phosphoric acid ester and a phosphonic acid ester in an amount to make the polycarbonate flame-retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant polycarbonate composition. More specifically, it relates to a flame-retardant polycarbonate composition having excellent heat resistance and heat stability and improved safety.

[0002]

2. Description of the Related Art Conventionally, polycarbonates obtained by reacting a carbonate precursor with 2,2-bis (4-hydroxyphenyl) propane are excellent in transparency, heat resistance, mechanical properties and dimensional stability. Widely used in many fields as engineering plastics.
In particular, it has many uses as an optical material because of its excellent transparency. However, with the recent trend toward smaller and lighter molded products, a new material having excellent heat resistance and flame retardancy, such as a lens used closer to a heat source, is desired. Also,
There is a demand for a resin having higher thermal stability and higher safety.

On the other hand, polycarbonates obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with a carbonate precursor are known, and are also known to have a high refractive index and good heat resistance. However, it has been found that polycarbonate obtained from the above 9,9-bis (4-hydroxyphenyl) fluorene may cause rash during molding, especially for people with weak skin.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to provide:
Provided is a flame-retardant polycarbonate composition having improved safety that does not cause rash at the time of molding while maintaining preferable characteristics of polycarbonate obtained from 9-bis (4-hydroxyphenyl) fluorene, that is, excellent heat resistance. It is in.

The inventor of the present invention has conducted intensive studies to achieve this object, and as a result, it has been found that a methyl group has been substituted at a specific position.
A polycarbonate composition obtained by using -bis (4-hydroxy-3-methylphenyl) fluorene and further combining a specific compound with a polycarbonate copolymer obtained by further using a specific amount of another dihydroxy component solves the above problem. They have found that this can be achieved and arrived at the present invention.

[0006]

SUMMARY OF THE INVENTION According to the present invention, there is provided a method for preparing an aromatic dihydroxy component comprising 5-95 mol% of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;
Mol% is the following general formula [1]

[0007]

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Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen; W is a single bond; 1 to
20 hydrocarbon groups which may contain an aromatic group, -O-,-
S -, - SO -, - SO 2 -, - CO- or -COO-
At least one compound selected from the group consisting of an organic sulfonate, an organic sulfate, a phosphoric acid ester and a phosphonic acid ester, to a polycarbonate copolymer comprising a dihydroxy component represented by the following formula: The present invention relates to a flame-retardant polycarbonate composition which is blended in a flame retarding amount.

In the polycarbonate copolymer of the present invention, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is used as an aromatic dihydroxy component. %, Preferably 7 to 85 mol%, more preferably 10 to
Advantageously, it is 75 mol%. If the amount is less than 5 mol%, the properties of the heat-resistant material, which is the object of the present invention, are unsatisfactory.

The other dihydroxy component used in the polycarbonate copolymer of the present invention may be any one which is usually used as a dihydroxy component of a polycarbonate, such as hydroquinone, resorcinol, 4,4'-biphenol, and 1,1. -Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4' -(M-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide,
Bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 4-hydroxyphenylbenzoic acid-4 '
-Hydroxyphenyl ester, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, bis (3-
Bromo-4-hydroxyphenyl) sulfone, bis (4
-Hydroxy-3-methylphenyl) sulfide and the like, and among them, 2,2-bis (4-hydroxyphenyl) propane is preferable.

The polycarbonate copolymer is prepared by dissolving 0.7 g of the polymer in 100 ml of methylene chloride and heating at 20 ° C.
Those having a specific viscosity of 0.17 to 0.95 measured in the above are preferable, and those having a specific viscosity in the range of 0.25 to 0.71 are more preferable.
If the specific viscosity is less than 0.17, the molded article becomes brittle,
If it is higher, the melt viscosity and the solution viscosity increase, which makes it difficult to handle.

The polycarbonate copolymer of the present invention is produced by a reaction means known per se for producing ordinary polycarbonate, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or a carbonic acid diester. Next, basic means of these manufacturing methods will be briefly described. In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. At that time, the reaction temperature is usually 0 to 40.
° C and the reaction time is a few minutes to 5 hours.

The transesterification using a carbonic acid diester as a carbonate precursor is a method in which a predetermined ratio of an aromatic dihydroxy component is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill off the alcohol or phenols formed. It is performed by The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols produced by reducing the pressure from the beginning. Further, a catalyst usually used in a transesterification reaction to promote the reaction can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

In the polymerization reaction of the polycarbonate copolymer of the present invention, monofunctional phenols which are usually used as a terminal stopper can be used. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminating agent for controlling the molecular weight, and the obtained polycarbonate copolymer has a monofunctional phenol having a terminal at the end. Since it is blocked by a group based on, it has better thermal stability than that which is not. The monofunctional phenol may be any one used as a terminal terminator for polycarbonate, and is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula. it can.

[0015]

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Wherein A is a hydrogen atom or a carbon number of 1 to 9,
It is preferably 1 to 8 aliphatic hydrocarbon groups, and r is 1 to
5, preferably an integer of 1 to 3]. Specific examples of such monofunctional phenols include, for example, phenol, pt
tert-butylphenol, p-cumylphenol, isooctylphenol and the like.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or an aliphatic polyester group as a substituent, or long-chain alkyl carboxylic acid chlorides can be used, and the ends of the polycarbonate copolymer can be used with these. When blocked, they not only function as a terminal terminator or a molecular weight regulator, but also improve the melt flowability of the resin and facilitate not only the molding process but also the physical properties of the product. Particularly, it has an effect of lowering the water absorption of the resin, and is preferably used. These are represented by the following general formula [I
-A] to [Ih].

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[In each formula, X is -RO-, -R-CO-
O- or -RO-CO-, wherein R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms; And n is an integer of 10 to 50. Q is a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, p is an integer of 0 to 4, and Y is 1 to 10 carbon atoms, preferably 1 to 5 is a divalent aliphatic hydrocarbon group, and W ¹ is a hydrogen atom, —CO—R ¹¹ , —CO—O
—R ¹² or R ¹³ , wherein R ¹¹ , R ¹² and R ¹³ each are a monovalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, 4 to 8 carbon atoms, preferably 5 to 6 monovalent alicyclic hydrocarbon group or 6 to 15 carbon atoms, preferably 6 to 1
2 monovalent aromatic hydrocarbon groups. a is an integer of 4 to 20, preferably 5 to 10, m is an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, Z is a single bond or a carbon number of 1 to 10, Preferably 1 to 5
W ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and a carbon atom having 4 to 8, preferably 5 to 6 carbon atoms. A monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 15, preferably 6 to 12 carbon atoms]

Of these, preferred are the substituted phenols [Ia] and [Ib]. This [Ia]
As the substituted phenols, n is 10 to 30, particularly 10
-26 are preferred, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and tricontylphenol. Further, as the substituted phenols of [Ib], X is -R-
Compounds in which R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof are decyl hydroxybenzoate and dodecyl hydroxybenzoate. , Tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. In the substituted phenols or substituted benzoyl chlorides represented by the general formulas [Ia] to [Ig], the position of the substituent is generally preferably the p-position or the o-position, and a mixture of both is preferable.

It is desirable that the monofunctional phenol is introduced into at least 5 mol%, preferably at least 10 mol%, of all terminals of the obtained polycarbonate copolymer. Is alone or 2
You may mix and use more than one kind. In the polycarbonate copolymer of the present invention, when 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is 60 mol% or more of the total aromatic hydroxy component, the fluidity of the resin is reduced. Therefore, the above general formula [I
It is preferable to use substituted phenols or substituted benzoyl chlorides represented by -a] to [Ig] as a terminal stopper. The polycarbonate copolymer of the present invention,
Its glass transition point is preferably 155 ° C. or higher, and 160 ° C.
The above is more preferable, and the temperature is more preferably 165 ° C or higher.

In the present invention, at least one of a sulfonate, an organic sulfate, a phosphate and a phosphonate selected from the group consisting of sulfonates, organic sulfates, phosphates and phosphonates is added to the polycarbonate copolymer in an amount imparting flame retardancy. Is compounded.

As the sulfonates and organic sulfates, conventionally known aromatic sulfonates and organic sulfates are used. Among them, potassium benzenesulfonate, sodium and potassium sulfonates of diphenyl sulfone, and sodium lauryl sulfate are used. Is particularly preferred. The amount of the sulfonate or the organic sulfate is an amount capable of imparting flame retardancy to the polycarbonate copolymer,
It is selected from a wide range depending on the desired flame retardancy.
Usually, 0.001 to polycarbonate copolymer
1.0% by weight, preferably 0.003 to 0.1% by weight, and particularly preferably 0.005 to 0.05% by weight. If the amount is less than 0.001% by weight, it is difficult to obtain a flame-retardant effect. If the amount exceeds 1.0% by weight, the heat stability of the polycarbonate composition is adversely affected, which is not preferable.

The at least one phosphorus compound selected from the group consisting of phosphate esters and phosphonate esters preferably has the following general formulas [2] and [3]:

[0032]

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[0033]

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At least one phosphorus compound selected from the group consisting of: Here, R ^{5 to} R ¹⁰ are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl,
C1-C20 alkyl groups such as butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, and C6 carbon atoms such as phenyl, tolyl, and naphthyl
To 15 aryl groups or aralkyl groups having 7 to 18 carbon atoms such as benzyl and phenethyl. When two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring.

Examples of the phosphorus compound represented by the general formula [2] include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, and the like.
Diisopropyl phosphate, sodium bis (4-t
tert-butylphenyl) phosphate, 12H-dibenzo [d, g] [1.3.2] dioxaphosphosine-
2,4,8,10-tetrakis (tert-butyl)-
And sodium salts of 6-hydroxy-6-oxide [NA-11 manufactured by Adeka Argus Co., Ltd.]. Examples of the phosphorus compound represented by the general formula [3] include dimethyl benzenephosphonate and benzenephosphonic acid. Diethyl and dipropyl benzenephosphonate. Among them, triphenyl phosphate, sodium bis (4-tert-butylphenyl) phosphate, NA
-11, dimethyl benzenephosphonate is preferably used.

The compounding amount of the phosphorus compound is an amount capable of imparting flame retardancy to the polycarbonate copolymer, and is selected from a wide range depending on the desired flame retarding performance. Normal,
0.1 to 10% by weight based on the polycarbonate copolymer
And preferably from 0.2 to 8% by weight, particularly preferably from 0.5 to 7% by weight. If the amount is less than 0.1% by weight, the flame retardant effect is hardly obtained, and if it exceeds 10% by weight, the heat stability of the polycarbonate composition is adversely affected, which is not preferable.

The reason why such a flame retardant is particularly preferred in the composition of the present invention is not clear, but the copolymer of the present invention is particularly susceptible to carbonization because it has a group having a large amount of aromatic components such as a fluorene skeleton. It seems to be due to.

The polycarbonate composition of the present invention may contain a conventionally known antioxidant for the purpose of preventing oxidation. Examples thereof include phosphite-based or phenol-based antioxidants. Specifically, for example, triphenyl phosphite, tris nonyl phenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophosphite Phenyl phosphite, dioctyl monophenyl phosphite diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert
-Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, triethylene glycol
Bis [3- (3-tert-butyl-5-methyl-4-
Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t
tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10- Tetraoxaspiro (5
5) Undecane and the like. The preferable range of the addition amount of these antioxidants is 0.0001 to 0.05% by weight based on the polycarbonate copolymer.

Further, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the polycarbonate composition of the present invention, if necessary. By blending the higher fatty acid ester of the monohydric or polyhydric alcohol, the releasability from the mold at the time of molding the polycarbonate composition is improved. Deformation of the disk substrate and pit shift due to defects can be prevented. There is also an advantage that the melt fluidity of the polycarbonate composition is improved. The higher fatty acid ester is preferably a partial ester or a whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Examples of the partial or total ester of a monohydric or polyhydric alcohol and a saturated fatty acid include monoglyceride stearate, monosorbitate stearate, monoglyceride behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, Propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, etc., among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferred Used.
The amount of the ester of the alcohol and the higher fatty acid is 0.01 to 2% by weight, preferably 0.015 to 0.5% by weight, based on the polycarbonate copolymer.
0.02 to 0.2% by weight is more preferred. The blending amount is 0.
If the amount is less than 01% by weight, the above effect cannot be obtained. If the amount exceeds 2% by weight, the mold surface becomes soiled, which is not preferable.

The polycarbonate composition of the present invention further comprises a light stabilizer, a colorant, an antistatic agent, a lubricant, a glass fiber,
Additives such as inorganic fillers such as carbon fibers and metal fibers can be added. Also, other polycarbonate resins,
A thermoplastic resin may be added within a range that does not impair the object of the present invention. Further, in order to enhance the flame retardancy, conventionally known halogen-based flame retardants, flame-retardant assistants, fluorine compound-based and / or siloxane-based anti-drip agents can be added.

The polycarbonate composition of the present invention can be produced by any method. For example, a method of mixing with a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used. The polycarbonate composition is molded by any method such as an injection molding method, a compression molding method, an extrusion molding method, and a solution casting method.

[0043]

The present invention will be further described with reference to the following examples. In the examples, parts and% are parts by weight and% by weight, respectively. (1) Specific viscosity: 0.7 g of a polymer was dissolved in 100 ml of methylene chloride and measured at 20 ° C. (2) Glass transition point (Tg): 910 type D manufactured by DuPont
It was measured by SC.

[Synthesis Example 1] In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 24623 parts of ion-exchanged water and 4153 parts of a 48% aqueous sodium hydroxide solution were charged.
After dissolving 635 parts of bis- (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "biscresolfluorene"), 3444 parts of bisphenol A and 8 parts of hydrosulfite, 18188 parts of methylene chloride are added. Phosgene 1 at 15-25 ° C. with stirring
994 parts were blown in over 60 minutes. After the injection of phosgene was completed, a solution prepared by dissolving 100.7 parts of p-tert-butylphenol in 1330 parts of methylene chloride and 692.1 parts of a 48% aqueous sodium hydroxide solution were added and emulsified, and 5.8 parts of triethylamine was added. The reaction was completed by stirring at ~ 33 ° C for 1 hour. After the reaction was completed, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as ion-exchanged water,
The methylene chloride was evaporated in a kneader, and the ratio of biscresol fluorene to bisphenol A was 10: 9 in molar ratio.
As a result, 4284.5 parts (yield: 95%) of a colorless powdery polymer which was 0 was obtained. The specific viscosity of this polymer is 0.3
39, Tg was 165 ° C. This polymer is referred to as polycarbonate A.

Synthesis Example 2 Biscresol fluorene and bisphenol A were prepared in the same manner as in Synthesis Example 1 except that the amount of biscresol fluorene used in Synthesis Example 1 was changed to 3171.4 parts and the amount of bisphenol A was changed to 1913 parts. Of the polymer having a molar ratio of 50:50 (96% yield). The specific viscosity of this polymer is 0.32
0 and Tg was 205 ° C. This polymer is referred to as polycarbonate B.

Example 1 To 100 parts of the polycarbonate A obtained in Synthesis Example 1, 0.03 parts of tris (2,4-di-tert-butylphenyl) phosphite, 0.01 parts of trimethyl phosphate, and diphenylsulfone sulfone Potassium acid 0.01 part, octadecyl stearate 0.1.
3 parts were mixed with a Nauta mixer, and 280 ° C. with an extruder.
And pelletized. Its Tg was 164 ° C. After drying the pellets at 120 ° C. for 6 hours, a 1/16 inch thick UL-94 combustion test piece was injection molded using an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. At this time, none of the persons engaged in the molding had rash on the skin. When the flame retardancy was evaluated using this test piece according to UL-94, it was ranked V-2. The Tg of this product was 164 ° C.

Example 2 The flame retardancy was evaluated in the same manner as in Example 1 except that 0.01 part of sodium lauryl sulfate was used in place of potassium diphenylsulfonesulfonate of Example 1. Ranked. The Tg of this product was 164 ° C.

Example 3 59.4 parts of polycarbonate A of Synthesis Example 1 and ABS resin [UT-6 manufactured by Mitsui Toatsu Co., Ltd.]
1) Triphenyl phosphate 7 was added to 25 parts of the mixture.
Part, talc 8 parts, trimethyl phosphate 0.1 part, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate [A manufactured by Adeka Argus Co., Ltd.
O-18] 0.2 part and 2 (2'-hydroxy-5'-
After mixing 0.3 part of [tert-octylphenyl) benzotriazole [Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd.], the mixture was pelletized by an extruder. The pellet was formed into a combustion test piece in the same manner as in Example 1, and the flame retardancy was evaluated. Its Tg was 128 ° C.

Example 4 In place of polycarbonate A, 100 parts of polycarbonate B obtained in Synthesis Example 2 was used.
12H instead of potassium diphenylsulfonate
-Dibenzo [d, g] [1.3.2] dioxaphosphosine-2,4,8,10-tetrakis (tert-butyl) -6-hydroxy-6-oxide sodium salt [Adeka Argus Co., Ltd. ) NA-11] A combustion test piece was molded in the same manner as in Example 1 except that 0.01 part was used, and the flame retardancy was evaluated. The Tg of the product was 203 ° C.

Example 5 Instead of NA-11, 2,2
A combustion test piece was formed in the same manner as in Example 4 except that 0.02 part of -bis (3-bromo-4-sodium sulfopropoxyphenyl) propane was used and 0.3 part of fibril-forming polytetrafluoroethylene was used. When the flame retardant performance was evaluated, it was ranked V-0. The Tg of the product was 202 ° C.

[Comparative Example 1] A combustion test piece was molded in the same manner as in Example 1 except that potassium diphenylsulfonate was not used, and the flame retardancy was evaluated.

Comparative Example 2 A polymer was obtained in the same manner as in Synthesis Example 1 except that 588 parts of bisphenolfluorene was used instead of biscresolfluorene, to obtain 4066 parts of a polymer (yield: 91%). The specific viscosity of this polymer was 0.334 and the Tg was 183 ° C. The same additives as in Example 1 were similarly added to this, and a test piece was formed. As a result, some of the workers engaged in the formation of rash on the skin.

[Comparative Example 3] In Example 1, Synthesis Example 1
Bisphenol A instead of polycarbonate A obtained in
Polycarbonate (Tg 150 ° C, specific viscosity 0.4
Except for using 50), the molding was evaluated in the same manner as in Example 1, and the flame retardancy was rated V-2 by UL-94. Its Tg was 148 ° C.

Comparative Example 4 The procedure of Example 3 was repeated, except that the polycarbonate A powder of Comparative Example 3 was used instead of the polycarbonate A powder of Synthesis Example 1 of Example 3.
In the same manner as in the above, pellets were obtained. The Tg of this is 10
6 ° C., which is lower than that of Example 3 and inferior in heat resistance.

[0055]

Industrial Applicability The flame-retardant polycarbonate resin composition of the present invention has improved heat resistance and flame-retardant properties while preventing rashes during molding, while maintaining excellent heat resistance. Can be used as For example, optics suitable for structural or functional material use of optical components such as electrical and electronic components, optical discs, optical lenses, headlamp lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, displays, etc. It can be used advantageously as a molded article for use. Among these, it can be used particularly advantageously in fields requiring flame retardancy and heat resistance.

Claims (7)

[Claims] 1. A total aromatic dihydroxy component in which 5-95 mol% is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 95-5 mol% is in the following general formula [1]: [Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms or a halogen, W is a single bond, 1 to 20 carbon atoms. A hydrocarbon group which may contain an aromatic group, -O-, -S-, -SO
_{-, - SO 2 -, -} CO- or -COO- in which] the polycarbonate copolymer comprising a dihydroxy component represented by, organic sulfonates, organic sulfates, esters of esters of phosphoric and phosphonic acids A flame-retardant polycarbonate composition comprising at least one compound selected from the group consisting of a flame-retardant amount. 2. The organic sulfonate salt has 6 to 3 carbon atoms.
An aromatic sulfonic acid salt of 0 or an aliphatic sulfonic acid salt of 3 to 30 carbon atoms, and the compounding amount thereof is 0.001 to 1% by weight based on the polycarbonate copolymer.
The flame-retardant polycarbonate composition according to the above. 3. The organic sulfate according to claim 1, wherein the organic sulfate has 8 to 8 carbon atoms.
The flame-retardant polycarbonate composition according to claim 1, which is a sulfate ester salt of No. 30 in an amount of 0.001 to 1% by weight based on the polycarbonate copolymer. 4. An ester of phosphoric acid is represented by the following general formula [2]: Wherein R ^{5 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. May be formed. And at least one of R ^{5 to} R ⁷ is the above-mentioned hydrocarbon group].
The flame-retardant polycarbonate composition according to claim 1, which is 10% by weight. 5. The ester of a phosphonic acid is represented by the following general formula [3]: [Wherein, R ^{8 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.
⁸ at least one to R ¹⁰ is a phosphonic acid ester represented by a said hydrocarbon group], claim 1 the amount thereof is 0.1 to 10% by weight of the polycarbonate copolymer The flame-retardant polycarbonate composition according to the above. 6. The flame-retardant polycarbonate composition according to claim 1, wherein the dihydroxy component represented by the general formula [1] is 2,2-bis (4-hydroxyphenyl) propane. . 7. The polycarbonate copolymer according to claim 1,
20 g of a solution of 7 g in 100 ml of methylene chloride
The flame-retardant polycarbonate composition according to any one of claims 1 to 6, wherein the specific viscosity measured in (1) is in the range of 0.17 to 0.95.